Group 4 metal compound containing thiophene-fused cyclopentadienyl ligand derived from tetraquinoline derivative and olefin polymerization using the same

ABSTRACT

The present invention relates to a novel ligand derived from a tetrahydroquinoline derivative, and a transition metal compound prepared using the ligand, where an amido ligand is linked to an ortho-phenylene ligand to form a condensed ring and a 5-membered cyclic pi-ligand linked to the ortho-phenylene ligand is fused with a heterocyclic thiophene ligand. Compared with the catalysts not fused with a heterocyclic thiophene ligand, the transition metal compound of the present invention as activated with a co-catalyst has higher catalytic activity in olefin polymerization and provides a polymer with higher molecular weight.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority from and is a divisionalof U.S. Ser. No. 13/640,924, filed Apr. 24, 2013, which claims thebenefit of priority from and is a National Stage Entry ofPCT/KR2011/002580, filed Apr. 12, 2011, which claims the benefit ofpriority from Korean applications 10-2010-0033273, filed Apr. 12, 2010,and 10-2010-0057102, filed Jun. 16, 2010, the entire contents of whichare hereby incorporated.

FIELD OF THE INVENTION

The present invention relates to a novel transition metal compoundcontaining a thiophene-fused cyclopentadienyl moiety substituted at the8-position of a tetrahydroquinoline derivative and a method forpreparing an olefin polymer using the same, and more particularly to anovel transition metal compound having a cyclopentadienyl/amido groupbridged by an ortho-phenylene group and a method for preparing an olefinpolymer using the same.

BACKGROUND OF THE INVENTION

The early synthesis method for olefin polymer involves preparing a boroncompound of cyclopentenone and using the Suzuki-coupling reaction, asshown in the following Scheme 1. This method is, however, problematic inthat the boron compound is hard to synthesize, making the synthesismethod unsuitable for large-scaled manufacture, and that only a limitedrange of boron compounds can be prepared, consequently with difficultyin diversification of cyclopentadienyl ligands (Organometallics 2006,25, 2133; Dalton Trans. 2006, 4056; Organometallics 2006, 25, 5122;Dalton Trans. 2007, 4608; Organomet. Chem. 2008, 693, 457; J. Organomet.Chem. 2006, 691, 5626; Korean Patent Registration No. 10-843603; KoreanPatent Registration No. 10-0789241; Korean Patent Registration No.10-0789242; and Korean Patent Registration No. 10-0843603).

To solve this problem, there has been developed a new synthesis methodgiven by the following Scheme 2. The synthesis method in the Scheme 2advantageously provides an approach to preparing the desired ligand in asingle step and introduces a variety of 5-membered cyclic pi-ligands,such as indenyl or fluorenyl (Organometaalics, 2008, 27, 3907).

The following compound 1 or 2 prepared by this method is superior to theconventional CGC([Me₂Si(η⁵-Me₄C₅)(N^(t)Bu)]TiCl₂) catalyst developed byDow Chemical Corp. in terms of catalytic activity and copolymerizationcharacteristic, showing the possibility of its use in the commercialmanufacture process (Organometallics, 2007, 27, 6685; Macromolecules,2008, 42, 4055; Macromolecules, 2010, 43, 725; Korean PatentRegistration No. 820, 542; Korean Public Patent No. 08-0065868; andKorean Patent Registration No. 906,165). More specifically, the amidoligand is combined with the ortho-phenylene ligand to form a condensedring, which reduces the steric hindrance at the reaction site oftitanium to enhance reactivity.

Besides, transition metal compounds of 5-membered cyclic pi-ligandsfused with a heterocyclic compound containing nitrogen or sulfuratom(s), and an olefin polymerization reaction using the transitionmetal compounds have been occasionally reported. But, there has neverbeen a report on the transition metal compounds coordinated with5-membered cyclic pi-ligands fused with a heterocyclic compound amongthose compounds having a condensed ring formed with an amido ligand andan ortho-phenylene ligand like compound 1 or 2 (J. Am. Chem. Soc., 1998,120, 10786; J. Am. Chem. Soc., 2001, 123, 4763; Macromol. Chem. Phys.,2004, 205, 302; Angew. Chem. Int. Ed., 2009, 48, 9871; Organometallics,2002, 21, 2842; J. Am. Chem. Soc., 2004, 126, 17040; Macromol. Chem.Phys., 2004, 205, 2275; Macromol. Chem. Phys., 2005, 206, 1405.Organometallics, 2004, 23, 344; J. Am. Chem. Soc., 2003, 125, 10913;Organometallics, 2009, 28, 6915; J. Organomet. Chem., 2005, 690, 4213;and U.S. Pat. No. 6,451,938).

Sustainable attempts have been made in the fields of academy andindustry to develop homogenous Ziegler-Natta catalysts since Prof.Kaminsky developed the homogeneous Ziegler-Natta catalyst using a Group4 metallocene compound activated with a methylaluminoxane co-catalyst inthe late 1970's (Kaminsky et al., Dalton Trans., 2009, 8803). It is theadvantage claimed for the homogenous Ziegler-Natta catalysts over theheterogeneous Ziegler-Natta catalysts that the homogeneous Ziegler-Nattacatalysts are excellent in α-olefin incorporation in ethylene/α-olefincopolymerization and provide a uniform α-olefin distribution. Theconventional heterogeneous catalysts in ethylene/α-olefincopolymerization not only provide a low quantity of α-olefinincorporation but cause the α-olefin incorporation to occur primarily inthe polymer chain with low molecular weight only. On the other hand, thedisadvantage of the homogeneous catalysts is that they cannot provide apolymer with high molecular weight. In contrast to the conventionalheterogeneous Ziegler-Natta catalysts which are used to form a polymerchain with high molecular weight, the homogeneous catalysts can be usedonly to produce a polymer chain with a molecular weight of no more thanabout 100,000. With low molecular weight, the polymers encounter alimitation in development of their usage, such as being inapplicable tothe products required to have high strength. For that reason, theconventional heterogeneous Ziegler-Natta catalysts have been used in theindustrial manufacture of polymers, and the use of the homogeneouscatalysts is confined to the manufacture for some grades of polymer. Itis therefore the ultimate object to overcome such a fundamentallimitation by developing a homogeneous catalyst excellent in α-olefinreactivity and capable of producing polymers with high molecular weight.

In an attempt to solve the problems with the prior art, the inventors ofthe present invention have discovered a novel ligand in which an amidoligand is linked to an ortho-phenylene ligand to form a condensed ring,and a 5-membered pi-ligand combined with the ortho-phenylene ligand isfused with a heterocyclic thiophene ligand, and found it out that thecatalyst comprising a transition metal compound prepared from the novelligand has higher catalytic activity and provides a polymer with highermolecular weight than the catalyst not fused with a heterocyclicthiophene ligand, thereby completing the present invention.

DISCLOSURE OF INVENTION Technical Problem

It is therefore a first object of the present invention to provide anovel transition metal compound which contains fused ring with aheterocyclic thiophene ligand.

It is a second object of the present invention to provide a precursorfor the transition metal compound that is the novel ligand.

It is a third object of the present invention to provide a method forpreparing a precursor for the transition metal compound.

It is a fourth object of the present invention to provide a catalystcomposition comprising the novel transition metal compound.

It is a fifth object of the present invention to provide a method forpreparing an olefin polymer using the novel transition metal compound.

Technical Solution

To achieve the first object of the present invention, there is provideda transition metal compound represented by the following formula 1:

In the formula 1, M is a Group 4 transition metal;

Q¹ and Q² are independently halogen, C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl,C₂-C₂₀ alkynyl, C₆-C₂₀ aryl, C₁-C₂₀ alkyl C₆-C₂₀ aryl, C₆-C₂₀ arylC₁-C₂₀ alkyl, C₁-C₂₀ alkylamido, C₆-C₂₀ arylamido, or C₁-C₂₀ alkylidene;

R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independently hydrogen;C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; C₂-C₂₀alkenyl with or without an acetal, ketal, or ether group; C₁-C₂₀ alkylC₆-C₂₀ aryl with or without an acetal, ketal, or ether group; C₆-C₂₀aryl C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; orC₁-C₂₀ silyl with or without an acetal, ketal, or ether group, where R¹and R² can be linked to each other to form a ring; R³ and R⁴ can belinked to each other to foam a ring; and at least two of R⁵ to R¹⁰ canbe linked to each other to form a ring; and

-   -   R¹¹, R¹², and R¹³ are independently hydrogen; C₁-C₂₀ alkyl with        or without an acetal, ketal, or ether group; C₂-C₂₀ alkenyl with        or without an acetal, ketal, or ether group; C₁-C₂₀ alkyl C₆-C₂₀        aryl with or without an acetal, ketal, or ether group; C₆-C₂₀        aryl C₁-C₂₀ alkyl with or without an acetal, ketal, or ether        group; C₁-C₂₀ silyl with or without an acetal, ketal, or ether        group; C₁-C₂₀ alkoxy; or C₆-C₂₀ aryloxy, where R¹¹ and R¹², or        R¹² and R¹³ can be linked to each other to form a ring.

To achieve the second object of the present invention, there is provideda precursor for the transition metal compound of the formula 1 asrepresented by the following formula 2:

In the formula 2, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² andR¹³ are as defined above.

To achieve the third object of the present invention, there is provideda method for preparing a precursor for transition metal compound asrepresented by the following formula 2, the method comprising: (a)reacting a tetrahydroquinoline derivative represented by the followingformula 3 with alkyl lithium and adding carbon dioxide to prepare acompound represented by the following formula 4; and (b) reacting thecompound of the formula 4 with alkyl lithium, adding a compoundrepresented by the following formula 5, and then treating with an acid:

In the formulas 2, 3, 4 and 5, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰,R¹¹, R¹², R¹³ are as defined above.

To achieve the fourth object of the present invention, there is provideda catalyst composition comprising: a transition metal compoundrepresented by the following formula 1; and at least one co-catalystcompound selected from the group consisting of compounds represented bythe following formula 6, 7, or 8:

In the formula 1, M, Q¹, Q², R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰,R¹¹, R¹², and R¹³ are as defined above.

—[Al(R⁶¹)—O]_(a)—  [Formula 6]

In the formula 6, R⁶¹ is independently a halogen radical, a C₁-C₂₀hydrocarbyl radical, or a halogen-substituted C₁-C₂₀ hydrocarbylradical; and a is an integer of 2 or above.

D(R⁷¹)₃  [Formula 7]

In the formula 7, D is aluminum (Al) or boron (B); and R⁷¹ isindependently a halogen radical, a C₁-C₂₀ hydrocarbyl radical, or ahalogen-substituted C₁-C₂₀ hydrocarbyl radical.

[L-H]⁺[Z(A)₄]⁻ or [L]⁺[Z(A)₄]⁻  [Formula 8]

In the formula 8, L is a neutral or cationic Lewis acid; Z is a Group 13element; and A is independently a C₆-C₂₀ aryl or C₁-C₂₀ alkyl radicalhaving at least one hydrogen atom substituted with a halogen radical, aC₁-C₂₀ hydrocarbyl radical, a C₁-C₂₀ alkoxy radical, or a C₆-C₂₀ aryloxyradical.

To achieve the fifth object of the present invention, there is provideda method for preparing a polyolefin by polymerizing an olefin-basedmonomer in the presence of the catalyst composition.

Advantageous Effects

When activated with the known co-catalyst, the novel transition metalcompound provided by the present invention exhibits high catalyticactivity and good copolymerization characteristic in olefinpolymerization, resulting in production of a polymer with high molecularweight, so it can be readily used in commercial manufacture to prepare apolymer of different grades. Particularly, the transition metal compoundof the present invention is advantageous over the catalysts not fusedwith a heterocyclic thiophene ligand in that it has higher catalyticactivity and provides a polymer with higher molecular weight.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is an illustration showing the structure of a transition metalcompound (the compound E-4 of Example 9) according to one embodiment ofthe present invention.

FIG. 2 is an illustration showing the structure of a transition metalcompound (the compound E-2 of Example 7) according to another embodimentof the present invention.

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, a description will be given as to a catalyst for olefinpolymerization, and a method for preparing a polyolefin using the sameaccording to the embodiments of the present invention.

In the course of repeated studies on catalysts for olefinpolymerization, the inventors of the present invention have discovered anovel ligand in which an amido ligand is linked to an ortho-phenyleneligand to form a condensed ring, and a 5-membered cyclic pi-ligandlinked to the ortho-phenylene ligand is fused with a heterocyclicthiophene ligand. Also, they have found it out that a transition metalcompound comprising the ligand exhibits higher catalytic activity andprovides a polymer with higher molecular weight than a transition metalcompound not fused with a heterocyclic thiophene ligand.

In accordance with one embodiment of the present invention, there isprovided a transition metal compound represented by the followingformula 1:

In the formula 1, M is a Group 4 transition metal; Q¹ and Q² areindependently a halogen, C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl,C₆-C₂₀ aryl, C₁-C₂₀ alkyl C₆-C₂₀ aryl, C₆-C₂₀ aryl C₁-C₂₀ alkyl, C₁-C₂₀alkylamido, C₆-C₂₀ arylamido, or C₁-C₂₀ alkylidene;

R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independently hydrogen;C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; C₂-C₂₀alkenyl with or without an acetal, ketal, or ether group; C₁-C₂₀ alkylC₆-C₂₀ aryl with or without an acetal, ketal, or ether group; C₆-C₂₀aryl C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; orC₁-C₂₀ silyl with or without an acetal, ketal, or ether group, where R¹and R² can be linked to each other to form a ring; R³ and R⁴ can belinked to each other to form a ring; and at least two of R⁵ to R¹⁰ canbe linked to each other to form a ring; and

R¹¹, R¹², and R¹³ are independently hydrogen; C₁-C₂₀ alkyl with orwithout an acetal, ketal, or ether group; C₂-C₂₀ alkenyl with or withoutan acetal, ketal, or ether group; C₁-C₂₀ alkyl C₆-C₂₀ aryl with orwithout an acetal, ketal, or ether group; C₆-C₂₀ aryl C₁-C₂₀ alkyl withor without an acetal, ketal, or ether group; C₁-C₂₀ silyl with orwithout an acetal, ketal, or ether group; C₁-C₂₀ alkoxy; or C₆-C₂₀aryloxy, where R¹¹ and R¹², or R¹² and R¹³ can be linked to each otherto form a ring.

With a substituent, including an acetal group, a ketal group, or anether group, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³are useful in the preparation of a silica-supported catalyst, asdisclosed in Korean Patent Registration No. 354,290 and Macromolecules2000, 33, 3194. The use of at least one functional group selected fromacetal, ketal, and ether groups does not interfere with the catalystsynthesis method of the present invention.

Compared with the catalyst not fused with a heterocyclic thiopheneligand, the catalyst for olefin polymerization using the transitionmetal compound represented by the formula 1 has higher catalyticactivity to reduce the cost for catalysts in the preparation of resinsand enables production of a polymer with higher molecular weight withoutsignificant deterioration in the α-olefin copolymerizationcharacteristics. Such a catalyst having good α-olefin copolymerizationcharacteristics and providing a polymer chain with high molecular weightis the ultimate aim of the development of homogeneous catalysts. Withthe development of olefin polymerization catalysts using the transitionmetal compound of the formula 1, it is possible to prepare polyolefingrades with various properties, which cannot be synthesized with theexisting heterogeneous catalysts.

In the transition metal compound represented by the formula 1, M ispreferably titanium (Ti), zirconium (Zr), or hafnium (Hf).

Preferably, Q¹ and Q² are independently halogen or C₁-C₂₀ alkyl. Morepreferably, Q¹ and Q² are independently chlorine or methyl.

R¹, R², R³, R⁴, and R⁵ are independently hydrogen or C₁-C₂₀ alkyl,preferably hydrogen or methyl. More preferably, R¹, R², R³, R⁴, and R⁵are independently hydrogen or methyl, with the provision that at leastone of R³ and R⁴ is methyl; and R⁵ is methyl.

Preferably, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ are independentlyhydrogen.

The transition metal compound of the formula 1 preferably includes theabove-mentioned substituents with a view to controlling the electronicand steric environments around the metal.

In accordance with another embodiment of the present invention, there isprovided a precursor for the transition metal compound of the formula 1as represented by the following formula 2:

In the formula 2, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ areindependently hydrogen; C₁-C₂₀ alkyl with or without an acetal, ketal,or ether group; C₂-C₂₀ alkenyl with or without an acetal, ketal, orether group; C₁-C₂₀ alkyl C₆-C₂₀ aryl with or without an acetal, ketal,or ether group; C₆-C₂₀ aryl C₁-C₂₀ alkyl with or without an acetal,ketal, or ether group; or C₁-C₂₀ silyl with or without an acetal, ketal,or ether group, where R¹ and R² can be linked to each other to form aring; R³ and R⁴ can be linked to each other to form a ring, and at leasttwo of R⁵ to R¹⁰ can be linked to each other to form a ring; and

R¹¹, R¹², and R¹³ are independently hydrogen; C₁-C₂₀ alkyl with orwithout an acetal, ketal, or ether group; C₂-C₂₀ alkenyl with or withoutan acetal, ketal, or ether group; C₁-C₂₀ alkyl C₆-C₂₀ aryl with orwithout an acetal, ketal, or ether group; C₆-C₂₀ aryl C₁-C₂₀ alkyl withor without an acetal, ketal, or ether group; C₁-C₂₀ silyl with orwithout an acetal, ketal, or ether group; C₁-C₂₀ alkoxy; or C₆-C₂₀aryloxy, where R¹¹ and R¹², or R¹² and R¹³ can be linked to each otherto form a ring.

In the precursor for the transition metal compound by the formula 2, R¹,R², R³, R⁴, and R⁵ are independently hydrogen or C₁-C₂₀ alkyl,preferably hydrogen or methyl. More preferably, R¹, R², R³, R⁴, and R⁵are independently hydrogen or methyl, with the provision that at leastone of R³ and R⁴ is methyl; and R⁵ is methyl.

Preferably, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ are independentlyhydrogen.

In accordance with further another embodiment of the present invention,there is provided a method for preparing the precursor for transitionmetal compound represented by the formula 2, the method comprising: (a)reacting a tetrahydroquinoline derivative represented by the followingformula 3 with alkyl lithium and adding carbon dioxide to prepare acompound represented by the following formula 4; and (b) reacting thecompound of the formula 4 with alkyl lithium, adding a compoundrepresented by the following formula 5, and then treating with an acid:

In the formulas 2, 3, 4 and 5, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, andR¹⁰ are independently hydrogen; C₁-C₂₀ alkyl with or without an acetal,ketal, or ether group; C₂-C₂₀ alkenyl with or without an acetal, ketal,or ether group; C₁-C₂₀ alkyl C₆-C₂₀ aryl with or without an acetal,ketal, or ether group; C₆-C₂₀ aryl C₁-C₂₀ alkyl with or without anacetal, ketal, or ether group; or C₁-C₂₀ silyl with or without anacetal, ketal, or ether group, where R¹ and R² can be linked to eachother to form a ring; R³ and R⁴ can be linked to each other to form aring, and at least two of R⁵ to R¹⁰ can be linked to each other to forma ring; and

R¹¹, R¹², and R¹³ are independently hydrogen; C₁-C₂₀ alkyl with orwithout an acetal, ketal, or ether group; C₂-C₂₀ alkenyl with or withoutan acetal, ketal, or ether group; C₁-C₂₀ alkyl C₆-C₂₀ aryl with orwithout an acetal, ketal, or ether group; C₆-C₂₀ aryl C₁-C₂₀ alkyl withor without an acetal, ketal, or ether group; C₁-C₂₀ silyl with orwithout an acetal, ketal, or ether group; C₁-C₂₀ alkoxy; or C₆-C₂₀aryloxy, where R¹¹ and R¹², or R¹² and R¹³ can be linked to each otherto form a ring.

The step (a) involves reacting a tetrahydroquinoline derivative of theformula 3 with alkyl lithium and then adding carbon dioxide to form acompound of the formula 4, which process can be achieved by the methodsdisclosed in the known documents (Tetrahedron Lett. 1985, 26, 5935;Tetrahedron 1986, 42, 2571; and J. Chem. SC. Perkin Trans. 1989, 16).

In the step (b), the compound of the formula 4 is reacted with alkyllithium to activate deprotonation and produce an ortho-lithium compound,which is then reacted with a compound of the formula 5 and treated withan acid to obtain a precursor for transition metal compound of theformula 2.

The method of producing an ortho-lithium compound by reaction betweenthe compound of the formula 4 and alkyl lithium is disclosed in knowndocuments (Organometallics 2007, 27,6685; and Korean Patent RegistrationNo. 2008-0065868). In the present invention, the ortho-lithium compoundis reacted with a compound of the formula 5 to produce a precursor fortransition metal compound of the formula 2.

The compound of the formula 5 can be prepared by a variety of knownmethods. For example, the following Scheme 3 can be used to prepare theprecursor for the transition metal compound of the present inventionwith ease in a one-step process, which is economically beneficial byusing inexpensive starting materials (J. Organomet. Chem., 2005, 690,4213).

On the other hand, a variety of known methods can be employed tosynthesize the transition metal compound of the formula 1 from theprecursor for transition metal compound of the formula 2 obtained by theabove-stated preparation method. The most common method of preparing thetransition metal compound of the formula 1 involves adding 2 equivalentsof alkyl lithium to the precursor for transition metal compound of theformula 2 to induce deprotonation for producing a dilithium compound ofcyclopentadienyl anion and amide anion, and then adding (Q¹)(Q²)MCl₂ toeliminate 2 equivalents of LiCl.

Another method involves reacting the compound of the formula 2 withM(NMe₂)₄ to eliminate 2 equivalents of HNME₂ and produce a transitionmetal compound of the formula 1, where both Q¹ and Q² are NMe₂, and thenadding Me₃SiCl or Me₂SiCl₂ to replace the NMe₂ ligand with a chlorineligand.

In the compound of the formula 2, R¹, R², R³, R⁴, and R⁵ areindependently hydrogen or C₁-C₂₀ alkyl, preferably hydrogen or methyl.More preferably, R¹, R², R³, R⁴, and R⁵ are independently hydrogen ormethyl, with the provision that at least one of R³ and R⁴ is methyl; andR⁵ is methyl. Preferably, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ areindependently hydrogen. In this regard, the precursor of the formula 2with the above-mentioned substituents is desirable in terms ofaccessibility of a starting material and advantageous with a view tocontrolling the electronic and steric environments for the desiredtransition metal compound of the formula 1.

The preparation method for the transition metal compound is describedmore specifically with reference to the following examples.

In accordance with still another embodiment of the present invention,there is provided a catalyst composition comprising: a transition metalcompound represented by the following formula 1; and at least oneco-catalyst compound selected from the group consisting of compoundsrepresented by the following formula 6, 7, or 8:

In the formula 1, M, Q¹, Q², R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰,R¹¹, R¹², and R¹³ are as defined above.

—[Al(R⁶¹)—O]_(a)—  [Formula 6]

In the formula 6, R⁶¹ is independently a halogen radical, a C₁-C₂₀hydrocarbyl radical, or a halogen-substituted C₁-C₂₀ hydrocarbylradical; and a is an integer of 2 or above.

D(R⁷¹)₃  [Formula 7]

In the formula 7, D is aluminum (Al) or boron (B); and R⁷¹ isindependently a halogen radical, a C₁-C₂₀ hydrocarbyl radical, or ahalogen-substituted C₁-C₂₀ hydrocarbyl radical.

[L-H]⁺[Z(A)₄]⁻ or [L]⁺[Z(A)₄]⁻  [Formula 8]

In the formula 8, L is a neutral or cationic Lewis acid; Z is a Group 13element; and A is independently a C₆-C₂₀ aryl or C₁-C₂₀ alkyl radicalhaving at least one hydrogen atom substituted with a halogen radical, aC₁-C₂₀ hydrocarbyl radical, a C₁-C₂₀ alkoxy radical, or a C₆-C₂₀ aryloxyradical.

The compounds represented by the formula 6, 7, or 8 are widely used as aco-catalyst for the homogeneous Ziegler-Natta catalyst comprising ametallocene compound.

In the catalyst composition, the molar ratio (Ti:Al) of the co-catalystcompound of the formula 6 to the transition metal compound is preferably1:100 to 1:20,000, more preferably 1:500 to 1:5,000.

The molar ratio (Ti:D) of the co-catalyst compound of the formula 7 tothe transition metal compound, where D is boron (B), is preferably 1:1to 1:10, more preferably 1:1 to 1:3. The molar ratio (Ti:D), where D isaluminum (Al), depends on the amount of water in the polymerizationsystem and is preferably 1:1 to 1:1,000, more preferably 1:1 to 1:100.

The molar ratio (Ti:Z) of the co-catalyst compound of the formula 8 tothe transition metal compound is preferably 1:1 to 1:10, more preferably1:1 to 1:4.

In the catalyst composition, the molar ratio of the co-catalyst compoundto the transition metal compound below the lower limit of the definedrange possibly leads to failure to acquire the catalytic activity, whilethe molar ratio above the upper limit of the defined range increases theexpense of the co-catalyst in preparation of resins.

In terms of the efficiency in activating the transition metal compoundof the formula 1, the substituents are given as follows: in the formula6, R⁶¹ is methyl; in the formula 7, D is aluminum (Al), and R⁷¹ ismethyl or isobutyl; or D is boron (B), and R⁷¹ is pentafluorophenyl; andin the formula 8, [L-H]⁺ is a dimethylanilinium cation, [Z(A)₄]⁻ is[B(C₆F₅)₄]⁻, and [L]⁺ is [(C₆H₅)₃C]⁺.

In accordance with still another embodiment of the present invention,there is provided a method for preparing a polyolefin by polymerizing anolefin-based monomer in the presence of the catalyst composition.

The polyolefin can be prepared by reacting the catalyst composition withat least one olefin-based monomer. The olefin-based monomer is notspecifically limited and preferably includes at least one monomerselected from the group consisting of ethylene, propylene, 1-butene,1-hexene, 1-octene, and 1-decene.

The preparation method for polyolefin is more specifically described inthe following examples of the present invention.

Hereinafter, a detailed description will be given as to the presentinvention in accordance with the preferred embodiments, which are givenby way of illustration only and not intended to limit the scope of thepresent invention.

The synthesis procedures for the precursor and the transition metalcompound were performed in the atmosphere of inert gas, such as nitrogenor argon, according to the following Schemes 4 and 5, using the standardSchlenk and glove box techniques.

The individual compounds in the Scheme 4 come in different substituents.The substituents are presented in the table given below thecorresponding compound (for example, the compound D-2 denotes a compoundhaving a hydrogen atom for R^(a) and a methyl group for R^(b) andR^(c).).

In the Scheme 4, the compound C (C-1, C-2, or C-3) was synthesized by aknown method (J. Organomet. Chem., 2005, 690, 4213).

Synthesis of Precursor and Transition Metal Compound Example 1 Synthesisof Precursor D-1

A Schlenk flask containing 1,2,3,4-tetrahydroquinoline (1.00 g, 7.51mmol) and diethyl ether (16 ml) was cooled down in a cold bath at −78°C. and stirred while n-butyl lithium (3.0 mL, 7.5 mmol, 2.5 M hexanesolution) was slowly added under the nitrogen atmosphere. After one-houragitation at −78° C., the flask was gradually warmed up to the roomtemperature. A light yellowish solid precipitated, and the butane gaswas removed through a bubbler. The flask was cooled down back to −78° C.and supplied with carbon dioxide. Upon injection of carbon dioxide, theslurry-type solution turned to a clear homogenous solution. Afterone-hour agitation at −78° C., the flask was gradually warmed up to −20°C. while the extra carbon dioxide was removed through the bubbler toremain a white solid as a precipitate.

Tetrahydrofuran (0.60 g, 8.3 mmol) and t-butyl lithium (4.9 mL, 8.3mmol, 1.7 M pentane solution) were sequentially added at −20° C. in thenitrogen atmosphere, and the flask was agitated for about 2 hours.Subsequently, a tetrahydrofuran solution (19 mL) containing lithiumchloride and the compound C-1 (1.06 g, 6.38 mmol) was added in thenitrogen atmosphere. The flask was agitated at −20° C. for one hour andthen gradually warmed up to the room temperature. After one-houragitation at the room temperature, water (15 mL) was added to terminatethe reaction. The solution was moved to a separatory funnel to extractthe organic phase. The extracted organic phase was put in a separatoryfunnel, and then hydrochloric acid (2 N, 40 mL) was added. After shakingthe solution for about 2 minutes, an aqueous solution of sodiumhydrocarbonate (60 mL) was slowly added to neutralize the solution. Theorganic phase was separated and removed of water with anhydrousmagnesium sulfate to eliminate the solvent and yield a sticky product.The product thus obtained was purified by the silica gel columnchromatography using a mixed solvent of hexane and ethylacetate (v/v,50:1) to yield 77.2 mg of the desired compound (43% yield).

In the ¹H NMR spectrum of the final product, there was observed a set oftwo signals at ratio of 1:1, resulting from the difficulty of rotatingabout the carbon-carbon bond (marked as a thick line in the Scheme 4)between phenylene and cyclopentadiene. In the following ¹³C NMRspectrum, the values in parenthesis are chemical shift values split dueto the difficulty of rotation.

¹H NMR (C₆D₆): δ 7.22 and 7.17 (br d, J=7.2 Hz, 1H), 6.88 (s, 2H), 6.93(d, J 7.2 Hz, 1H), 6.73 (br t, J=7.2 Hz, 1H), 3.84 and 3.80 (s, 1H, NH),3.09 and 2.98 (q, J=8.0 Hz, 1H, CHMe), 2.90-2.75 (br, 2H, CH₂),2.65-2.55 (br, 2H, CH₂), 1.87 (s, 3H, CH₃), 1.70-1.50 (m, 2H, CH₂), 1.16(d, J=8.0 Hz, 3H, CH₃) ppm.

¹³C NMR (C₆D₆): 151.64 (151.60), 147.74 (147.61), 146.68, 143.06,132.60, 132.30, 129.85, 125.02, 121.85, 121.72, 119.74, 116.87, 45.86,42.54, 28.39, 22.89, 16.32, 14.21 ppm.

Example 2 Synthesis of Precursor D-2

The procedures were performed in the same manner as described in thesynthesis of the compound D-1 in Example 1, excepting that the compoundC-2 was used rather than the compound C-1. The yield was 53%.

In the ¹H NMR spectrum of the final product, there was observed a set oftwo signals at ratio of 1:1, resulting from the difficulty of rotatingabout the carbon-carbon bond (marked as a thick line in the Scheme 4)between phenylene and cyclopentadiene.

¹H NMR (C₆D₆): δ 7.23 (d, J=7.2 Hz, 1H), 6.93 (d, J=7.2 Hz, 1H), 6.74(br t, J=7.2 Hz, 1H), 4.00 and 3.93 (s, 1H, NH), 3.05 (br q, J=8.0 Hz,1H, CHMe), 3.00-2.80 (br, 2H, CH₂), 2.70-2.50 (br, 2H, CH₂), 2.16 (s,3H, CH₃), 2.04 (br s, 3H, CH₃), 1.91 (s, 3H, CH₃), 1.75-1.50 (m, 2H,CH₂), 1.21 (d, J=8.0 Hz, 3H, CH₃) ppm.

¹³C NMR (C₆D₆): 151.60 (151.43), 145.56 (145.36), 143.08, 141.43,132.90, 132.68, 132.43, 129.70, 121.63, 120.01, 116.77, 46.13, 42.58,28.42, 22.97, 15.06, 14.19, 14.08, 12.70 ppm.

Example 3 Synthesis of Precursor D-3

The procedures were performed in the same manner as described in thesynthesis of the compound D-1 in Example 1, excepting thattetrahydroquinaldine was used rather than tetrahydroquinoline. The yieldwas 63%.

In the ¹H NMR spectrum of the final product, a certain signal was splitinto a set of four signals at ratio of 1:1:1:1, resulting from thedifficulty of rotating about the carbon-carbon bond (marked as a thickline in the Scheme 4) between phenylene and cyclopentadiene andisomerism pertaining to the existence of two chiral centers.

¹H NMR (C₆D₆): δ 7.33, 7.29, 7.22, and 7.17 (d, J=7.2 Hz, 1H), 6.97 (d,J=7.2 Hz, 1H), 6.88 (s, 2H), 6.80-6.70 (m, 1H), 3.93 and 3.86 (s, 1H,NH), 3.20-2.90 (m, 2H, NCHMe, CHMe), 2.90-2.50 (m, 2H, CH₂), 1.91, 1.89,and 1.86 (s, 3H, CH₃), 1.67-1.50 (m, 1H, CH₂), 1.50-1.33 (m, 1H, CH₂),1.18, 1.16, and 1.14 (s, 3H, CH₃), 0.86, 0.85, and 0.80 (d, J=8.0 Hz,3H, CH₃) ppm.

¹³C NMR (C₆D₆): 151.67, 147.68 (147.56, 147.38), 147.06 (146.83, 146.28,146.10), 143.01 (142.88), 132.99 (132.59), 132.36 (131.92), 129.69,125.26 (125.08, 124.92, 124.83), 122.03, 121.69 (121.60, 121.28), 119.74(119.68, 119.46), 117.13 (117.07, 116.79, 116.72), 47.90 (47.73), 46.04(45.85), 31.00 (30.92, 30.50), 28.00 (27.83, 27.64), 23.25 (23.00),16.38 (16.30), 14.63 (14.52, 14.18) ppm.

Example 4 Synthesis of Precursor D-4

The procedures were performed in the same manner as described in thesynthesis of the compound D-1 in Example 1, excepting that the compoundC-2 and tetrahydroquinaldine were used rather than the compound C-1 andtetrahydroquinoline. The yield was 63%.

In the ¹H NMR spectrum of the final product, a certain signal was splitinto a set of four signals at ratio of 1:1:1:1, resulting from thedifficulty of rotating about the carbon-carbon bond (marked as a thickline in the Scheme 4) between phenylene and cyclopentadiene andisomerism pertaining to the existence of two chiral centers.

¹H NMR (C₆D₆): δ 7.32, 7.30, 7.22, and 7.19 (d, J=7.2 Hz, 1H), 6.97 (d,J=7.2 Hz, 1H), 6.85-6.65 (m, 1H), 4.10-3.90 (s, 1H, NH), 3.30-2.85 (m,2H, NCHMe, CHMe), 2.85-2.50 (m, 2H, CH₂), 2.15 (s, 3H, CH₃), 2.02 (s,3H, CH₃), 1.94, 1.92, and 1.91 (s, 3H, CH₃), 1.65-1.50 (m, 1H, CH₂),1.50-1.33 (m, 1H, CH₂), 1.22, 1.21, 1.20, and 1.19 (s, 3H, CH₃),1.10-0.75 (m, 3H, CH₃) ppm.

¹³C NMR (C₆D₆): 151.67 (151.57), 145.58 (145.33, 145.20), 143.10(143.00, 142.89), 141.62 (141.12), 134.08 (133.04), 132.84 (132.70,136.60), 132.50 (132.08), 129.54, 121.52 (121.16), 119.96 (119.71),117.04 (116.71), 47.90 (47.78), 46.29 (46.10), 31.05 (30.53), 28.02(28.67), 23.37 (23.07), 15.22 (15.04), 14.87 (14.02, 14.21), 12.72(12.67) ppm.

Example 5 Synthesis of Precursor D-5

The procedures were performed in the same manner as described in thesynthesis of the compound D-1 in Example 1, excepting that the compoundC-3 and tetrahydroquinaldine were used rather than the compound C-1 andtetrahydroquinoline. The yield was 48%.

In the ¹H NMR spectrum of the final product, a certain signal was splitinto a set of four signals at ratio of 1:1:1:1, resulting from thedifficulty of rotating about the carbon-carbon bond (marked as a thickline in the Scheme 4) between phenylene and cyclopentadiene andisomerism pertaining to the existence of two chiral centers.

¹H NMR (C₆D₆): δ 7.32, 7.29, 7.22 and 7.18 (d, J=7.2 Hz, 1H), 6.96 (d,J=7.2 Hz, 1H), 6.84-6.68 (m, 1H), 6.60 (d, J=7.2 Hz, 1H), 4.00-3.92 (s,1H, NH), 3.30-2.90 (m, 2H, NCHMe, CHMe), 2.90-2.55 (m, 2H, CH₂), 2.27(s, 3H, CH₃), 1.94, 1.91 and 1.89 (s, 3H, CH₃), 1.65-1.54 (m, 1H, CH₂),1.54-1.38 (m, 1H, CH₂), 1.23, 1.22, and 1.20 (s, 3H, CH₃), 1.00-0.75 (m,3H, CH₃) ppm.

¹³C NMR (C₆D₆): 151.51, 145.80, 145.64, 145.45, 144.40, 144.22, 143.76,143.03, 142.91, 139.78, 139.69, 139.52, 133.12, 132.74, 132.52, 132.11,129.59, 121.52, 121.19, 120.75, 120.47, 119.87, 119.69, 116.99, 116.76,47.90, 47.77, 46.43, 46.23, 32.55, 30.98, 30.51, 27.95, 27.67, 23.67,23.31, 23.06, 16.52, 15.01, 14.44, 14.05 ppm.

Example 6 Synthesis of Transition Metal Compound E-1

In a dry box, the compound D-1 (0.10 g, 0.36 mmol) synthesized inExample 1 and dimethyl ether were put into a round-bottomed flask andcooled down to −30° C. N-butyl lithium (2.5 M hexane solution, 0.2 g,0.71 mmol) was gradually added to the flask under agitation to activatethe reaction at −30° C. for 2 hours. Warmed up to the room temperature,the flask was agitated for more 3 hours for the reaction. After cooleddown back to −30° C., to the flask were added methyl lithium (1.6 Mdiethyl ether solution, 0.33 g, 0.71 mmol) and then TiCl₄.DME (DME:dimethoxyethane, 0.10 g, 0.36 mmol). The flask, while warmed up to theroom temperature, was agitated for 3 hours and then removed of thesolvent using a vacuum line. Pentane was used to extract the compound.The removal of the solvent produced 0.085 g of the final compound as abrownish powder (60% yield).

¹H NMR (C₆D₆): δ 7.09 (d, J=7.2 Hz, 1H), 6.91 (d, J=7.2 Hz, 1H), 6.81(t, J=7.2 Hz, 1H), 6.74 (s, 2H), 4.55 (dt, J=14, 5.2 Hz, 1H, NCH₂), 4.38(dt, J=14, 5.2 Hz, 1H, NCH₂), 2.50-2.30 (m, 2H, CH₂), 2.20 (s, 3H), 1.68(s, 3H), 1.68 (quintet, J=5.2 Hz, CH₂), 0.72 (s, 3H, TiMe), 0.38 (s, 3H,TiMe) ppm.

¹³C{¹H} NMR (C₆D₆): 161.46, 142.43, 140.10, 133.03, 130.41, 129.78,127.57, 127.34, 121.37, 120.54, 120.51, 120.34, 112.52, 58.50, 53.73,49.11, 27.59, 23.27, 13.19, 13.14 ppm.

Example 7 Synthesis of Transition Metal Compound E-2

The procedures were performed in the same manner as described in thesynthesis of the compound E-1 in Example 6, excepting that the compoundD-2 was used rather than the compound D-1. The yield was 53%. Thestructure of the transition metal compound E-2 is shown in FIG. 2.

¹H NMR (C₆D₆): δ 7.10 (d, J=7.2 Hz, 1H), 6.91 (d, J=7.2 Hz, 1H), 6.81(t, J=7.2 Hz, 1H), 4.58 (dt, J=14, 5.2 Hz, 1H, NCH₂), 4.42 (dt, J=14,5.2 Hz, 1H, NCH₂), 2.50-2.38 (m, 2H, CH₂), 2.32 (s, 3H), 2.11 (s, 3H),2.00 (s, 3H), 1.71 (s, 3H), 1.67 (quintet, J=5.2 Hz, CH₂), 0.72 (s, 3H,TiMe), 0.38 (s, 3H, TiMe) ppm.

¹³C{¹H} NMR (C₆D₆): 161.58, 141.36, 138.41, 137.20, 132.96, 129.70,127.53, 127.39, 126.87, 121.48, 120.37, 120.30, 113.23, 56.50, 53.13,49.03, 27.64, 23.34, 14.21, 13.40, 12.99, 12.94 ppm. Anal. Calc.(C₂₂H₂₇NSTi): C, 68.56; H, 7.06; N, 3.63. Found: C, 68.35 H, 7.37 N,3.34%.

Example 8 Synthesis of Transition Metal Compound E-3

The procedures were performed in the same manner as described in thesynthesis of the compound E-1 in Example 6, excepting that the compoundD-3 was used rather than the compound D-1. The yield was 51%. The finalproduct was identified as a 1:1 mixture (the direction of the thiophenecyclic radical to the direction of the methyl radical ontetrahydroquinoline).

¹H NMR (C₆D₆): δ 7.11 and 7.08 (d, J=7.2 Hz, 1H), 6.96 and 6.95 (d,J=7.2 Hz, 1H), 6.82 and 6.81 (t, J=7.2 Hz, 1H), 6.77 and 6.76 (d, J=7.2Hz, 1H), 6.74 and 6.73 (d, J=7.2 Hz, 1H), 5.42 (m, 1H, NCH), 2.75-2.60(m, 1H, CH₂), 2.45-2.25 (m, 1H, CH₂), 2.24 and 2.18 (s, 3H), 1.73 and1.63 (s, 3H), 1.85-1.50 (m, 2H, CH₂), 1.17 and 1.15 (d, J=4.8 Hz, 3H),0.76 and 0.70 (s, 3H, TiMe), 0.42 and 0.32 (s, 3H, TiMe) ppm.

¹³C{¹H} NMR (C₆D₆): 159.58, 159.28, 141.88, 141.00, 139.63, 138.98,134.45, 130.85, 130.50, 129.59, 129.50, 129.47, 127.23, 127.20, 127.17,127.11, 120.77, 120.70, 120.40, 120.00, 119.96, 119.91, 118.76, 118.57,113.90, 110.48, 59.61, 56.42, 55.75, 51.96, 50.11, 49.98, 27.41, 27.11,21.89, 20.09, 19.67, 12.94, 12.91, 12.65 ppm.

Example 9 Synthesis of Transition Metal Compound E-4

The procedures were performed in the same manner as described in thesynthesis of the compound E-1 in Example 6, excepting that the compoundD-4 was used rather than the compound D-1. The yield was 57%. The finalproduct was identified as a 1:1 mixture (the direction of the thiophenecyclic radical to the direction of the methyl radical ontetrahydroquinoline). The structure of the transition metal compound E-4is shown in FIG. 1.

¹H NMR (C₆D₆): δ 7.12 and 7.10 (d, J=7.2 Hz, 1H), 6.96 and 6.94 (d,J=7.2 Hz, 1H), 6.82 and 6.81 (t, J=7.2 Hz, 1H), 5.45 (m, 1H, NCH),2.75-2.60 (m, 1H, CH₂), 2.45-2.20 (m, 1H, CH₂), 2.34 and 2.30 (s, 3H),2.10 (s, 3H), 1.97 (s, 3H), 1.75 and 1.66 (s, 3H), 1.85-1.50 (m, 2H,CH₂), 1.20 (d, J=6.8 Hz, 3H), 0.76 and 0.72 (s, 3H, TiMe), 0.44 and 0.35(s, 3H, TiMe) ppm.

¹³C{¹H} NMR (C₆D₆): 160.13, 159.86, 141.33, 140.46, 138.39, 137.67,136.74, 134.83, 131.48, 129.90, 129.78, 127.69, 127.65, 127.60, 127.45,126.87, 126.81, 121.34, 121.23, 120.21, 120.15, 119.15, 118.93, 114.77,111.60, 57.54, 55.55, 55.23, 51.73, 50.43, 50.36, 27.83, 27.67, 22.37,22.31, 20.53, 20.26, 14.29, 13.51, 13.42, 13.06, 12.80 ppm.

Example 10 Synthesis of Transition Metal Compound E-5

The procedures were performed in the same manner as described in thesynthesis of the compound E-1 in Example 6, excepting that the compoundD-5 was used rather than the compound D-1. The yield was 57%. The finalproduct was identified as a 1:1 mixture (the direction of the thiophenecyclic radical to the direction of the methyl radical ontetrahydroquinoline).

¹H NMR (C₆D₆): δ 7.12 and 7.09 (d, J=7.2 Hz, 1H), 6.96 and 6.94 (d,J=7.2 Hz, 1H), 6.82 and 6.80 (t, J=7.2 Hz, 1H), 6.47 and 6.46 (d, J=7.2Hz, 1H), 6.45 and 6.44 (d, J=7.2 Hz, 1H), 5.44 (m, 1H, NCH), 2.76-2.60(m, 1H, CH₂), 2.44-2.18 (m, 1H, CH₂), 2.28 and 2.22 (s, 3H), 2.09 (s,3H), 1.74 and 1.65 (s, 3H), 1.88-1.48 (m, 2H, CH₂), 1.20 and 1.18 (d,J=7.2 Hz, 3H), 0.77 and 0.71 (s, 3H, TiMe), 0.49 and 0.40 (s, 3H, TiMe)ppm.

¹³C{¹H} NMR (C₆D₆): 159.83, 159.52, 145.93, 144.90, 140.78, 139.93,139.21, 138.86, 135.26, 131.56, 129.69, 129.57, 127.50, 127.46, 127.38,127.24, 121.29, 121.16, 120.05, 119.96, 118.90, 118.74, 117.99, 117.74,113.87, 110.38, 57.91, 55.31, 54.87, 51.68, 50.27, 50.12, 34.77, 27.58,27.27, 23.10, 22.05, 20.31, 19.90, 16.66, 14.70, 13.11, 12.98, 12.68ppm.

Example 11 Synthesis of Transition Metal Compound E-6

The transition metal compound E-6 was synthesized according to thefollowing Scheme 5.

Methyl lithium (1.63 g, 3.55 mmol, 1.6 M diethyl ether solution) wasadded dropwise to a diethyl ether solution (10 mL) containing thecompound D-4 (0.58 g, 1.79 mmol). The solution was agitated overnight atthe room temperature and cooled down to −30° C. Then, Ti(NMe₂)₂Cl₂ (0.37g, 1.79 mmol) was added at once. After 3-hour agitation, the solutionwas removed of all the solvent with a vacuum pump. The solid thusobtained was dissolved in toluene (8 mL), and Me₂SiCl₂ (1.16 g, 8.96mmol) was added to the solution. The solution was agitated at 80° C. for3 days and removed of the solvent with a vacuum pump to obtain a reddishsolid compound (0.59 g, 75% yield). The ¹H NMR spectrum showed theexistence of two stereo-structural compounds at ratio of 2:1.

¹H NMR (C₆D₆): δ 7.10 (t, J=4.4 Hz, 1H), 6.90 (d, J=4.4 Hz, 2H), 5.27and 5.22 (m, 1H, NCH), 2.54-2.38 (m, 1H, CH₂), 2.20-2.08 (m, 1H, CH₂),2.36 and 2.35 (s, 3H), 2.05 and 2.03 (s, 3H), 1.94 and 1.93 (s, 3H),1.89 and 1.84 (s, 3H), 1.72-1.58 (m, 2H, CH₂), 1.36-1.28 (m, 2H, CH₂),1.17 and 1.14 (d, J=6.4, 3H, CH₃) ppm.

¹³C{¹H} NMR (C₆D₆): 162.78, 147.91, 142.45, 142.03, 136.91, 131.12,130.70, 130.10, 128.90, 127.17, 123.39, 121.33, 119.87, 54.18, 26.48,21.74, 17.28, 14.46, 14.28, 13.80, 13.27 ppm.

Preparation of Polyolefin Examples 12 to 15 Ethylene/1-HexeneCopolymerization Using Catalyst Compound Containing One of TransitionMetal Compounds E-1 to E-4 Activated with MAO

A toluene solution of 1-hexene co-monomer (0.30 M, 1-hexene 0.76 g, 30mL) was put into a high-pressure polymerization reactor in a dry box.Taken out of the dry box, the reactor was warmed up to 90° C. Each (0.50μmol) of the compounds E-1 to E-4 synthesized in Examples 6 to 9 wasmixed with methylaluminoxane (MAO) (7% Al toluene solution, 0.96 g, 2.5mmol Al, Al/Ti=5,000) and further with toluene to make the total volumeof the solution as 2 mL, thereby preparing an activated catalystcomposition. The zirconium compound was insoluble in toluene butdissolved in combination with the methylaluminoxane (MAO). The activatedcatalyst composition thus obtained was injected into the reactor througha syringe. Then, ethylene was injected under pressure of 60 prig for5-minute polymerization. The ethylene gas was ventilated, and 30 mL ofacetone was added to terminate the reaction. The white solid thusobtained was filtered out and dried in a vacuum oven at 100° C. for onehour.

The polymerization results are presented in Table 1.

The compound E-3 in Example 14 had a high catalytic activity to yield1.2 g of the desired polymer under the above-defined conditions. Thecopolymerization in this case is not desirable because almost all the1-hexene was used up. Hence, the polymerization reaction was carried outfor 2.5 minutes. The results are presented in Table 1.

The compound E-4 in Example 15 had an extremely high activity, leadingto undesirable polymerization to yield 1.9 g of the desired polymer.Even when the polymerization time was reduced to a half, i.e., 2.5minutes, the yielded amount of the product was 1.3 g, which resulted inundesired polymerization with extreme concentration gradient of1-hexene. Finally, 0.88 g of the desired polymer was yielded whenreducing the amount of the catalyst to 2.5 μmol and the polymerizationtime to 2.5 minutes. The polymerization results are presented in Table1.

Example 16 Ethylene/1-Hexene Copolymerization Using Catalyst CompoundContaining Transition Metal Compound E-4 Activated with TriisobutylAluminum and [PhC₃]⁺[B(C₆F₅)₄]⁻

The transition metal compound E-4 (0.50 μmol) was dissolved in toluene,and [PhC₃]⁺[B(C₆F₅)₄]⁻ (1.8 mg, 2.0 μmol, B/Ti=4) and triisobutylaluminum (40 mg, 0.2 mmol) were sequentially added to the solution,which was then stood for 5 minutes. The catalyst composition thusactivated was added into the reactor through a syringe. Then, theprocedures for polymerization reaction were performed in the same manneras described in Examples 12 to 15 to yield the final polymer compound.The polymerization results are presented in Table 1.

Comparative Example 1 Ethylene/1-Hexene Copolymerization Using CatalystCompound Containing Compound “a” Activated with MAO

For comparison with the catalyst disclosed in Korean Patent RegistrationNo. 820,542 and Korean Patent Publication No. 2008-65868 according tothe prior art, the procedures for polymerization reaction were performedin the same manner as described in Examples 12 to 15, excepting that thefollowing compound “a” was used.

Comparative Example 2 Ethylene/1-Hexene Copolymerization Using CatalystCompound Containing Compound “a” Activated with Triisobutyl Aluminum and[PhC₃]⁺[B(C₆F₅)₄]⁻

The procedures for polymerization reaction were performed in the samemanner as described in Example 16, excepting that the compound “a” wasused as in Comparative Example 1. The polymerization results arepresented in Table 1.

TABLE 1 Transition metal Yield of compound Polymerization polyolefin[Hex]^(b) (μmol) time (min) (g) Activity^(a) (mol %) Mw^(c) Mw/MnExample 12 Compound E-1 5.0 ~0 ~0 (0.50) Example 13 Compound E-2 5.00.66 16 26 20000 2.2 (0.50) Example 14 Compound E-3 2.5 0.85 41 27 250002.3 (0.50) Example 15 Compound E-4 2.5 0.88 84 22 54000 2.2 (0.25)Example 16^(d) Compound E-4 5.0 0.66 16 26 223000 2.5 (0.50) ComparativeCompound “a” 5.0 0.68 33 32 30000 2.0 Example 1 (0.25) ComparativeCompound “a” 5.0 0 .15 3.6 32 140000 2.1 Example 2 ^(d) (0.50)^(a)(activity) unit 10⁶ g/mol Ti • h ^(b)([Hex]) the quantity of1-hexene in polyolefin chain (¹H NMR spectroscopy) ^(c)(Mw) weightaverage molecular weight measured by GPC using polystyrene as areference ^(d)polymerization using [Ph₃C[[B(C₆F₅)₄] as a co-catalyst

As can be seen from the results of Table 1, the catalyst composition ofthe present invention had high catalytic activity and led to productionof a polymer with high molecular weight. Particularly, Examples 15 and16 showed excellences in terms of catalytic activity and molecularweight. The results also showed that the catalyst of the presentinvention had a catalytic activity at least 2.5 times higher andprovided a polymer with molecular weight at least 1.6 to 1.8 timehigher, demonstrating its considerable superiority to the conventionalcatalyst disclosed in Korean Patent Registration No. 820,542 and KoreanPatent Publication No. 2008-65868 according to the prior art.

Examples 17 to 22 Ethylene/1-Octene Copolymerization Using CatalystCompound Containing One of Transition Metal Compounds E-2 to E-6Activated with MAO

The procedures were performed in the same manner as described inExamples 12 to 15, using a toluene solution of 1-octene co-monomer (0.30M, 1-octene 1.0 g, 30 mL), any one (0.25 μmol) of the compounds E-2 toE-6, and methylaluminoxane (MAO) (7% Al toluene solution, 0.096 g,Al/Ti=1,000). Using a relatively small amount of MAO, (iBu)₃Al (0.20mmol, Al/Ti=800) was additionally put into the reactor through ascavenger. The polymerization results are presented in Table 2.

Example 23 Ethylene/1-Octene Copolymerization Using Catalyst CompoundContaining Transition Metal Compound E-4 Activated with TriisobutylAluminum and [PhC₃]⁺[B(C₆F₅)₄]⁻

The procedures were performed in the same manner as described in Example16, using a toluene solution of 1-octene co-monomer (0.30 M, 1-octene1.0 g, 30 mL), transition metal compound E-4 (0.25 μmol),[PhC₃]⁺[B(C₆F₅)₄]⁻ (1.0 μmol, B/Ti=4), and triisobutyl aluminum (0.20mmol, Al/Ti=800). The polymerization results are presented in Table 2.

Comparative Example 3 Ethylene/1-Octene Copolymerization Using CatalystCompound Containing Compound “a” Activated with MAO

The procedures for polymerization reaction were performed in the samemanner as described in Examples 17 to 22, excepting that the compound“a” was used as in Comparative Example 1. The polymerization results arepresented in Table 2.

TABLE 2 Transition metal Yield of compound Polymerization polyolefin[Oct]^(b) (μmol) time (min) (g) Activity^(a) (mol %) Mw^(c) Mw/MnExample 17 Compound E-2 3.0 0.20 16 22 132000 1.63 (0.25) Example 18Compound E-3 3.0 0.25 20 25 87000 1.62 (0.25) Example 19 Compound E-43.0 0.78 62 14 157000 1.60 (0.25) Example 20 Compound E-5 3.0 0.68 54 20153000 1.64 (0.25) Example 21 Compound E-6 3.0 0.63 50 22 152000 1.70(0.25) Example 22^(d) Compound E-4 3.0 0.91 36 21 104000 1.90 (0.50)Example 23^(e) Compound E-4 3.0 0.84 67 21 295000 1.73 (0.25)Comparative Compound “a” 3.0 0.18 11 34 91000 1.51 Example 3 (0.25)^(a)(activity) unit 10⁶ g/mol Ti • h ^(b)([Oct]) the quantity of1-hexene in polyolefin chain (¹H NMR spectroscopy) ^(c)(Mw) weightaverage molecular weight measured by GPC using polystyrene as areference ^(d)polymerization using hexane as a solvent and MAO (Al/Ti =500) as a co-catalyst ^(e)polymerization using [Ph₃C][B(C₆F₅)₄] as aco-catalyst

As can be seen from the results of Table 2, the catalyst composition ofthe present invention showed high catalytic activity and led toproduction of a polymer with high molecular weight under polymerizationconditions using a relative small amount of MAO which is highlyapplicable in industrial use. Particularly, as shown in Examples 19 to23, the compounds E-4, E-5, and E-6 showed high catalytic activity andenabled production of a polymer with high molecular weight. In relationto the catalyst composition of the present invention, the compound “a”of Comparative Example 3 as disclosed in Korean Patent Registration No.820,542 and Korean Patent Publication No. 2008-65868 according to theprior art had a relatively low activity (as low as about ⅕) and provideda polymer with relatively low molecular weight under polymerizationconditions using a smaller amount of MAO.

1. A precursor for transition metal compound represented by thefollowing formula 2:

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independentlyhydrogen; C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group;C₂-C₂₀ alkenyl with or without an acetal, ketal, or ether group; C₁-C₂₀alkyl C₆-C₂₀ aryl with or without an acetal, ketal, or ether group;C₆-C₂₀ aryl C₁-C₂₀ alkyl with or without an acetal, ketal, or ethergroup; or C₁-C₂₀ silyl with or without an acetal, ketal, or ether group,wherein R¹ and R² can be linked to each other to form a ring; R³ and R⁴can be linked to each other to form a ring, and at least two of R⁵ toR¹⁰ can be linked to each other to form a ring; and R¹¹, R¹², and R¹³are independently hydrogen; C₁-C₂₀ alkyl with or without an acetal,ketal, or ether group; C₂-C₂₀ alkenyl with or without an acetal, ketal,or ether group; C₁-C₂₀ alkyl C₆-C₂₀ aryl with or without an acetal,ketal, or ether group; C₆-C₂₀ aryl C₁-C₂₀ alkyl with or without anacetal, ketal, or ether group; C₁-C₂₀ silyl with or without an acetal,ketal, or ether group; C₁-C₂₀ alkoxy; or C₆-C₂₀ aryloxy, wherein R¹¹ andR¹², or R¹² and R¹³ can be linked to each other to form a ring.
 2. Theprecursor for transition metal compound as claimed in claim 1, whereinR¹, R², R³, R⁴, and R⁵ are independently hydrogen or methyl; and R⁶, R⁷,R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ are independently hydrogen.
 3. A methodfor preparing a precursor for transition metal compound represented bythe following formula 2, the method comprising: (a) reacting atetrahydroquinoline derivative represented by the following formula 3with alkyl lithium and adding carbon dioxide to prepare a compoundrepresented by the following formula 4; and (b) reacting the compound ofthe formula 4 with alkyl lithium, adding a compound represented by thefollowing formula 5, and then treating with an acid:

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independentlyhydrogen; C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group;C₂-C₂₀ alkenyl with or without an acetal, ketal, or ether group; C₁-C₂₀alkyl C₆-C₂₀ aryl with or without an acetal, ketal, or ether group;C₆-C₂₀ aryl C₁-C₂₀ alkyl with or without an acetal, ketal, or ethergroup; or C₁-C₂₀ silyl with or without an acetal, ketal, or ether group,wherein R¹ and R² can be linked to each other to form a ring; R³ and R⁴can be linked to each other to form a ring, and at least two of R⁵ toR¹⁰ can be linked to each other to form a ring; and R¹¹, R¹², and R¹³are independently hydrogen; C₁-C₂₀ alkyl with or without an acetal,ketal, or ether group; C₂-C₂₀ alkenyl with or without an acetal, ketal,or ether group; C₁-C₂₀ alkyl C₆-C₂₀ aryl with or without an acetal,ketal, or ether group; C₆-C₂₀ aryl C₁-C₂₀ alkyl with or without anacetal, ketal, or ether group; C₁-C₂₀ silyl with or without an acetal,ketal, or ether group; C₁-C₂₀ alkoxy; or C₆-C₂₀ aryloxy, wherein R¹¹ andR¹², or R¹² and R¹³ can be linked to each other to form a ring.
 4. Themethod as claimed in claim 3, wherein R¹, R², R³, R⁴, and R⁵ areindependently hydrogen or methyl; and R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², andR¹³ are independently hydrogen.